DE102005014638A1 - Substituted pyrazolyloxyphenyl derivatives as herbicides - Google Patents

Abstract

There are described Pyrazolyloxyphenylderivate the general formula (I) and their use as herbicides. DOLLAR F1 In this general formula (I), R 1, R 2 and R 3 are different radicals, and A is a cyclic radical selected from the group consisting of phenyl, pyridyl, thienyl and pyrazolyl.

Description

The The invention relates to the technical field of herbicides, in particular that of herbicides for the selective control of weeds and weeds in crops.

Out US 5698495 . US 5786392 WO 9718196 already discloses that certain pyrazolyloxyphenyl derivatives have herbicidal properties. WO 2003/051846 likewise describes pyrazolyloxyphenyl derivatives which carry a substituted radical bonded via an oxygen atom from the group consisting of phenyl, pyridyl, pyrazolyl and thienyl.

The However, compounds known from these publications often show one insufficient herbicidal activity. Task of the present The invention is therefore the provision of herbicidally active compounds with - opposite the compounds known from the prior art improved herbicidal properties.

worin die Substituenten und Indices folgende Bedeutungen haben:
R¹ bedeutet Wasserstoff, Brom, Chlor, Fluor, Iod oder Methylthio;
R² bedeutet Trifluormethyl, Difluormethyl oder Chlordifluormethyl
R³ bedeutet Methyl oder Ethyl;
A bedeutet einen Rest aus der Gruppe umfassend die Reste A1 bis A4

R⁴ bedeutet Fluormethyl, Difluormethyl, Trifluormethyl, Fluormethoxy, Difluormethoxy, Trifluormethyoxy, Chlor oder Cyano;
R⁵ bedeutet Wasserstoff, (C₁-C₈)-Alkyl, Brom, Chlor, Fluor, Iod oder Cyano, und
R⁶ bedeutet (C₁-C₈)-Alkyl.It has now been found that Pyrazolyloxyphenylderivate, which are substituted by selected radicals, are particularly suitable as herbicides. An object of the present invention are therefore compounds of formula (I) and their salts,

wherein the substituents and indices have the following meanings:
R ¹ is hydrogen, bromine, chlorine, fluorine, iodine or methylthio;
R ² is trifluoromethyl, difluoromethyl or chlorodifluoromethyl
R ³ is methyl or ethyl;
A is a radical from the group comprising the radicals A1 to A4

R ⁴ is fluoromethyl, difluoromethyl, trifluoromethyl, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chloro or cyano;
R ⁵ is hydrogen, (C ₁ -C ₈ ) -alkyl, bromine, chlorine, fluorine, iodine or cyano, and
R ⁶ is (C ₁ -C ₈ ) -alkyl.

ever according to the nature of the substituents the compounds of general formula (I) attach an acid, for example, hydrochloric acid. The resulting acid adducts, Like hydrochlorides, are also the subject of the invention.

In Formula (I) and all subsequent formulas may be alkyl radicals containing more than two carbon atoms be straight or branched. alkyl mean e.g. Methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, Hexyls such as n-hexyl, i-hexyl and 1,3-dimethylbutyl.

Depending on the nature and linkage of the substituents, the compounds of the general formula (I) can exist as stereoisomers. For example, if one or more asymmetric carbon atoms are present so, enantiomers and diastereomers can occur. Stereoisomers can be obtained from the mixtures obtained in the preparation by customary separation methods, for example by chromatographic separation methods. Similarly, stereoisomers can be selectively prepared by using stereoselective reactions using optically active sources and / or adjuvants. The invention also relates to all stereoisomers and mixtures thereof which include but are not specifically defined by the general formula (I).

Preference is given to compounds of the general formula (I) in which
R ¹ is hydrogen, bromine, chlorine, fluorine, iodine or methylthio;
R ² is trifluoromethyl or difluoromethyl;
R ³ is methyl or ethyl;
A is a radical from the group comprising the radicals A1 to A4;
R ⁴ is difluoromethyl trifluoromethyl, difluoromethoxy, trifluoromethoxy, chloro or cyano;
R ⁵ is hydrogen, fluorine or chlorine
R ⁶ is methyl or ethyl.

Particular preference is given to compounds of the general formula (I) in which
R ¹ is hydrogen, bromine, chlorine, fluorine or iodine;
R ² is trifluoromethyl or difluoromethyl;
R ³ is methyl or ethyl;
A is a radical from the group comprising the radicals A1 to A4;
R ⁴ is difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, chloro or cyano;
R ⁵ is hydrogen or fluorine;
R ⁶ is methyl.

Very particular preference is given to compounds of the general formula (I) in which
R ¹ is hydrogen, bromine, chlorine, fluorine or iodine, preferably bromine, chlorine, fluorine or iodine;
R ² is trifluoromethyl or difluoromethyl;
R ³ is methyl or ethyl;
A is the radical A1;
R ⁴ is difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, chloro or cyano;
R ⁵ is hydrogen or fluorine.

Also very particularly preferred are compounds of general formula (I) wherein
R ¹ is hydrogen, bromine, chlorine, fluorine or iodine, preferably bromine, chlorine, fluorine or iodine;
R ² is trifluoromethyl or difluoromethyl;
R ³ is methyl or ethyl;
A is the radical A2;
R ⁴ is difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, chloro or cyano.

Moreover, very particular preference is given to compounds of the general formula (I) in which
R ¹ is hydrogen, bromine, chlorine, fluorine or iodine, preferably, bromine, chlorine, fluorine or iodine;
R ² is trifluoromethyl or difluoromethyl;
R ³ is methyl or ethyl;
A is the radical A3;
R ⁴ is difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, chloro or cyano.

Likewise very particular preference is given to compounds of the general formula (I) in which
R ¹ is hydrogen, bromine, chlorine, fluorine or iodine, preferably bromine, chlorine, fluorine or iodine;
R ² is trifluoromethyl or difluoromethyl;
R ³ is methyl or ethyl;
A means the remainder A4;
R ⁴ is difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, chloro or cyano;
R ⁶ is methyl.

In all formulas below have the substituents and Symbols, unless otherwise defined, have the same meaning as in Formula (I) described.

Compounds of the formula (I) according to the invention can be prepared, for example, by the method given in Scheme 1. In this case, in a first step, the compound of the formula (II) ba seninduziert with a compound A-OH and then in a second step also base-induced with a compound (IIIa) to give compounds of formula (Ia), wherein R ^{1 is} nitro, reacted according to the invention. In compounds of the formulas (II) and (IIa), LG is in each case a leaving group, such as chlorine, fluorine or pseudohalogen. These reactions are known to the person skilled in the art. Scheme 1:

in the If necessary the two reaction steps mentioned above also in reverse Order performed become.

According to Scheme 2, compounds of the formula (Ia) according to the invention can be reacted to give compounds of the formula (Ib) according to the invention in which R ^{1 is} amino. These reactions are known to those skilled in the art for example from RL Augustine "Catalytic Hydrogenation" Marcel Dekker, New York 1965, Chpt5 and PN Rylander "Hydrogenation Methods" Academic Press, New York 1985, Chpt 8. Scheme 2:

• a) F.A. Carey, R.J. Sundberg, "Organische Chemie (Deutsche Ausgabe)" VCH Verlagsgesellschaft, Weinheim 1995, Chpt 24.2.1 und dort zitierte Literatur.
• b) Organikum, VEB Deutscher Verlag der Wissenschaften, Berlin 1988, Chpt D.8.2.1, D.8.3.1, D.8.3.2 und unter D.8.6. genannte Literaturhinweise.
• c) Schank K., Aromatic diazonium salts. Method. Chim. (1975), 6 159–203.
• d) Yoneda, Norihiko; Fukuhara, Tsuyoshi. Preparation of fluoro aromatics. Diazotization, fluorodediazoniation of amino aromatics. Yuki Gosei Kagaku Kyokaishi (1989), 47(7), 619–28.
• e) Nonhebel, Derek C. Copper-catalyzed single-electron oxidations and reductions. Special Publication – Chemical Society (1970), No. 24 409–37.

Schema 3:

Compounds of the invention of formula (Ic) wherein R ^{1a is} hydrogen, bromine, chlorine, fluorine, iodine or thiomethyl can be prepared according to Scheme 3 by diazotization and subsequent functionalization of the compounds (Ib). For example, these reactions are known to those skilled in the art from FA Carey, RJ Sundberg, "Organic Chemistry (German Edition)" VCH Verlagsgesellschaft, Weinheim 1995, Chpt 24.2.1, Yoneda, Norihiko; Fukuhara, Tsuyoshi: Preparation of fluoro aromatics. Diazotization-fluorodediazoniation of amino aromatics, Yuki Gosei Kagaku Kyokaishi (1989), 47 (7), 619-28. The diazotization of the aniline derivative (III) and functionalization of the diazonium salts (boiling and reduction, Schiemann reaction, Balz-Schiemann reaction, Sandmeyer reactions) are known in the art and can be carried out by known methods, see, for example

• a) FA Carey, RJ Sundberg, "Organic Chemistry (German Edition)" VCH Verlagsgesellschaft, Weinheim 1995, Chpt 24.2.1 and references cited therein.
• b) Organikum, VEB German publishing house of the sciences, Berlin 1988, Chpt D.8.2.1, D.8.3.1, D.8.3.2 and under D.8.6. cited references.
• c) Schank K., Aromatic diazonium salts. Method. Chim. (1975), 6159-203.
• d) Yoneda, Norihiko; Fukuhara, Tsuyoshi. Preparation of fluoro aromatics. Diazotization, fluorodediazonia tion of amino aromatics. Yuki Gosei Kagaku Kyokaishi (1989), 47 (7), 619-28.
• e) Non-lever, Derek C. Copper-catalyzed single-electron oxidations and reductions. Special Publication - Chemical Society (1970), no. 24 409-37.

Scheme 3:

The Compounds of the invention of the formula (I) have excellent herbicidal activity against a broad spectrum of economically important mono- and dikotyler Harmful plants. Also difficult to combat perennial weeds that from rhizomes, rhizomes or other permanent organs are eliminated by the active ingredients well recorded. It is usually irrelevant whether the substances in the pre-seed, Pre-emergence or Nachauflaufverfahren be applied. In detail be exemplary of some representatives of monocotyledonous and dicotyledonous weed flora called, controlled by the compounds of the invention can be without that through the mention a restriction to be done in certain ways. On the side of the monocots Weed species are e.g. Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria and Cyperus species from the annuelle group and on sides the perennial species Agropyron, Cynodon, Imperata and Sorghum and also well-endured Cyperus species.

at dicotyledonous weed species extends the spectrum of action on species such as. Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Sida, Matricaria and Abutilon on the annuelle Page as well as Convolvulus, Cirsium, Rumex and Artemisia at the perennial Weeds. Harmful plants occurring in rice under the specific culture conditions such as. Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus are also excellent in the active compounds according to the invention fought. Be the compounds of the invention before germination on the earth's surface applied, so either the emergence of the weed seedlings Completely prevents or the weeds grow up to the cotyledon stage, but then put her Growth and finally die completely after three to four weeks. For application the active ingredients on the greens Plant parts postemergence also occurs very quickly after the treatment a drastic halt in growth and the weed plants stay in the growth stage at the time of application stand or die completely after a certain time, so that on this Way one for the crops harmful Weed competition very early and sustainably eliminated. In particular, the compounds of the invention show a excellent effect against Apera spica venti, Chenopodium album, Lamium purpureum, Polygonum convulvulus, Stellaria media, Veronica hederifolia, Veronica persica and Viola tricolor.

Although the compounds of the invention have excellent herbicidal activity against mono- and dicotyledonous weeds, Crops of economically important crops, e.g. Wheat, barley, rye, rice, corn, sugar beet, cotton and soy only insignificant or not at all damaged. In particular, they have an excellent compatibility in cereals such as wheat, barley and maize, especially wheat.

The Present compounds are very suitable for these reasons good for selective control of undesirable Plant growth in agricultural crops or ornamental plantings.

Due to their herbicidal properties, the active compounds can also be used for controlling harmful plants in crops of known or yet to be developed genetically modified plants. The transgenic plants are usually characterized by particular advantageous properties, for example by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses. Other special properties relate to z. B. the crop in terms of quantity, quality, shelf life, composition and special ingredients. So are transgenic plants with increased starch content or altered quality of the starch or those with other fatty acid composition of the crop.

Prefers is the application of the compounds of the formula of the invention (I) or their salts in economically important transgenic cultures of useful and ornamental plants, eg. B. of cereals such as wheat, barley, Rye, oats, millet, rice, cassava and corn or even cultures of Sugar beet, Cotton, soya, rapeseed, potato, tomato, pea and other vegetables. Preferably the compounds of formula (I) as herbicides in crops be used, which opposite the phytotoxic effects of herbicides are resistant or genetically have been made resistant.

• – gentechnische Veränderungen von Kulturpflanzen zwecks Modifikation der in den Pflanzen synthetisierten Stärke (z. B. WO 92/11376, WO 92/14827, WO 91/19806),
• – transgene Kulturpflanzen, welche gegen bestimmte Herbizide vom Typ Glufosinate (vgl. z. B. EP-A-0242236, EP-A-242246) oder Glyphosate (WO 92/00377) oder der Sulfonylharnstoffe (EP-A-0257993, US-A-5013659) resistent sind,
• – transgene Kulturpflanzen, beispielsweise Baumwolle, mit der Fähigkeit Bacillus thuringiensis-Toxine (Bt-Toxine) zu produzieren, welche die Pflanzen gegen bestimmte Schädlinge resistent machen (EP-A-0142924, EP-A-0193259).
• – transgene Kulturpflanzen mit modifizierter Fettsäurezusammensetzung (WO 91/13972).

Conventional ways of producing new plants which have modified properties in comparison to previously occurring plants consist, for example, in classical breeding methods and the production of mutants. Alternatively, new plants with altered properties can be generated by genetic engineering techniques (see, eg, EP-A-0221044, EP-A-0131624). For example, several cases have been described

• Genetically engineered modifications of crops to modify the starch synthesized in the plants (eg WO 92/11376, WO 92/14827, WO 91/19806),
• Transgenic crops which are resistant to certain glufosinate-type herbicides (cf., for example, EP-A-0242236, EP-A-242246) or glyphosate (WO 92/00377) or the sulphonylureas (EP-A-0257993, US Pat. A-5013659) are resistant,
• - Transgenic crops, such as cotton, with the ability to produce Bacillus thuringiensis toxins (Bt toxins), which make the plants resistant to certain pests (EP-A-0142924, EP-A-0193259).
• Transgenic crops with modified fatty acid composition (WO 91/13972).

numerous molecular biology techniques that allow new transgenic plants with changed Properties can be produced are known in principle; see, e.g. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed. Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker "Gene and Clones ", VCH Weinheim 2nd edition 1996 or Christou, "Trends in Plant Science" 1 (1996) 423-431).

For such genetic manipulation can Nucleic acid molecules in plasmids introduced, the a mutagenesis or a sequence change by recombination of DNA sequences. With the help of the above Standard methods can z. B. Base exchanges made, partial sequences removed or natural or added synthetic sequences become. For the connection of the DNA fragments with each other can be linked to the fragments adapters or linker.

The Production of Plant Cells with Reduced Activity of a Gene product can be achieved, for example, by expression at least one corresponding antisense RNA, a sense RNA for Obtaining a Cosuppressionseffektes or expression at least a suitably engineered ribozyme that specifically transcripts of the above gene product cleaves.

For this can on the one hand, DNA molecules which uses the entire coding sequence of a gene product including possibly existing flanking sequences, as well DNA molecules which comprise only parts of the coding sequence, these parts have to be long enough to cause an antisense effect in the cells. Is possible also the use of DNA sequences that have a high degree of homology but not to the coding sequences of a gene product are completely identical.

at the expression of nucleic acid molecules in plants can synthesize the protein in any compartment be located in the plant cell. But the localization can be achieved in a particular compartment, z. B. the coding Region linked to DNA sequences which ensure localization in a particular compartment. Such sequences are known to the person skilled in the art (see, for example Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106).

The transgenic plant cells can be regenerated to whole plants by known techniques. The transgenic plants can in principle be plants of any plant species, i. both monocots as well as dicotyledonous plants.

So are transgenic plants available, the changed one Properties through overexpression, Suppression or inhibition of homologous (= natural) genes or gene sequences or expression of heterologous (= foreign) genes or gene sequences.

at the application of the active compounds according to the invention in transgenic cultures occur in addition to those observed in other cultures Opposite effects Harmful plants often have effects that apply to the application in the respective transgenic culture are specific, for example, a modified or specially extended weed spectrum that can be controlled can, changed Application rates for the application can be used, preferably good combinability with the herbicides, opposite which the transgenic culture is resistant, as well as influencing Growth and yield of transgenic crops. Subject of the invention is therefore also the use of the compounds of the invention as herbicides to combat of harmful plants in transgenic crops.

Furthermore have the substances according to the invention excellent growth regulatory properties in crops on. They regulate the plant's metabolism one and can thus for the targeted influencing of phytonutrients and for harvest relief, e.g. by triggering desiccation and stunted growth be used. Furthermore, they are also suitable for general Control and inhibition of unwanted vegetative growth without killing the plants. A Inhibition of vegetative growth plays in many mono- and dicots Cultures a big one Role, since the storage can be reduced or completely prevented.

The Compounds of the invention can in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the usual Preparations are applied. Another object of the invention are therefore herbicidal agents which are compounds of the formula (I) contain. The compounds of formula (I) can be formulated in various ways depending on which biological and / or chemical-physical parameters are pre-given. As formulation options, for example in question: wettable powder (WP), water-soluble powder (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions, Suspension concentrates (SC), dispersions based on oil or water, oil-miscible solutions, Capsule suspensions (CS), dusts (DP), mordant, granules for the spreading and soil application, granules (GR) in the form of micro-, spray, Elevator and adsorption granules, water-dispersible granules (WG), water-soluble Granules (SG), ULV formulations, microcapsules and waxes.

These individual formulation types are known and will be known in principle for example, described in: Winnacker-Kuchler, "Chemische Technologie", Volume 7, C. Hauser Publishing house Munich, 4th ed. 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying "Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.

The necessary formulation auxiliaries such as inert materials, surfactants, solvent and other additives are also known and are, for example described in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers ", 2nd ed., Darland Books, Caldwell N.J. H. V. Olphen, "Introduction to Clay Colloid Chemistry "; 2nd Ed., J. Wiley & Sons, N.Y .; C. Marsden, "Solvents Guide "; 2nd ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual ", MC Publ. Corp., Ridgewood N.J .; Sisley and Wood, "Encyclopedia of Surface Active Agents ", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Grenzflächenaktive Äthylenoxidaddukte", Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Kuchler, "Chemical Technology", Volume 7, C. Hauser Publishing house Munich, 4th ed. 1986.

wettable powder are uniformly dispersible in water Preparations, besides the active ingredient besides a dilution or inert or surfactants of ionic and / or nonionic nature (Wetting agent, dispersing agent), e.g. polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, Alkanesulfonates, alkylbenzenesulfonates, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, lignosulfonate sodium, dibutylnaphthalene-sulphonate sodium or also contain oleoylmethyltaurine acid sodium. For the production the spray powder, the herbicidal active ingredients, for example in usual Equipment such as hammer mills, Blower mills and Air-jet mills finely ground and simultaneously or subsequently with the formulation auxiliaries mixed.

Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent such as butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more ionic and / or nonionic surfactants (emulsifiers). As emulsifiers, for example alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide / ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters or polyoxethylenesorbitan esters such as polyoxyethylene sorbitan fatty acid esters.

dusts receives by grinding the active substance with finely divided solids, e.g. Talc, natural Clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.

suspension concentrates can water or oil based be. You can for example by wet grinding by means of commercial bead and optionally adding surfactants, such as those described e.g. above at the other formulation types are already listed.

emulsions e.g. Oil-in-water emulsions (EW), for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, such as those described e.g. above for the other formulation types already listed are, manufacture.

granules can either by atomizing of the active substance on adsorptive, granulated inert material or by application of active substance concentrates by means of adhesives, e.g. polyvinyl alcohol, Polyacrylic acid sodium or mineral oils, on the surface of excipients such as sand, kaolinite or granulated inert material. Also suitable Active ingredients in the the production of fertilizer granules usual Way - if desired in mixture with fertilizers - granulated.

Water-dispersible Granules are generally prepared by the usual methods such as spray drying, Fluidized bed granulation, plate granulation, mixing with high speed mixers and extrusion made without solid inert material.

to Production of plate, fluidized bed, Extruder and spray granules see, e.g. Procedure in "Spray Drying Handbook "3rd ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemical and Engineering 1967, p 147 ff; Perry's Chemical Engineer's Handbook, 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.

For further For details on the formulation of crop protection agents, see e.g. G.C. Klingman, "Weed Control as a Science ", John Wiley and Sons, Inc., New York, 1961, pp. 81-96 and J.D. Freyer, S.A. Evans, "Weed Control Handbook ", 5th ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

The agrochemical preparations usually contain from 0.1 to 99% by weight, in particular 0.1 to 95 wt .-%, active ingredient of the formula (I). In spray powders is the drug concentration e.g. about 10 to 90 wt .-%, the rest to 100 wt .-% consists of conventional Formulation components. For emulsifiable concentrates can the drug concentration is about 1 to 90, preferably 5 to 80 Wt .-% amount. Powdery Formulations contain 1 to 30 wt .-% of active ingredient, preferably usually 5 to 20 wt .-% of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt .-% of active ingredient. In the case of water-dispersible Granules hang the drug content depends in part on whether the active compound liquid or solid and which Granulierhilfsmittel, fillers etc. are used. For the water-dispersible granules if the content of active ingredient is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

Besides If necessary, the active substance formulations mentioned contain the each usual Adhesive, wetting, dispersing, emulsifying, penetrating, preserving, Antifreeze and solvents, filling, Carrier and Dyes, Defoamers, Evaporation inhibitor and the pH and the viscosity affecting Medium.

On The basis of these formulations can also be combined with other pesticidal substances, e.g. Insecticides, acaricides, Herbicides, fungicides, as well as with safeners, fertilizers and / or growth regulators produce, e.g. in the form of a ready-made formulation or as a tank mix.

Known active ingredients can be used as combination partners for the active compounds according to the invention in mixture formulations or in a tank mix, as described, for example, in Weed Research 26, 441-445 (1986) or "The Pesticide Manual", 11th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 1997 and cited there literature. Examples of known herbicides which can be combined with the compounds of the formula (I) are the following active substances (Note: The compounds are either with the "common name" according to the International Organization for Standardization (ISO) or with the chemical name , possibly together with a common code number):
acetochlor; acifluorfen; aclonifen; AKH 7088, ie methyl [[[1- [5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrophenyl] -2-methoxyethylidene] amino] oxy] acetic acid and acetic acid; alachlor; alloxydim; ametryn; amidosulfuron; aminopyralid; amitrol; AMS, ie ammonium sulfamate; anilofos; asulam; atrazine; azimsulfurones (DPX-A8947); aziprotryn; barban; BAS 516H, ie 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; benazolin; benfluralin; benfuresate; bensulfuron-methyl; bensulide; bentazone; benzofenap; benzofluor; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox; bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos; busoxinone; butachlor; butamifos; butenachlor; buthidazole; butraline; butylate; cafenstrole (CH-900); carbetamide; cafentrazone (ICI-A0051); CDAA, ie 2-chloro-N, N-di-2-propenylacetamide; CDEC, ie diethyldithiocarbamic acid 2-chloroallyl ester; chlomethoxyfen; chloramben; chloroazifop-butyl, chlorormesulone (ICI-A0051); chlorbromuron; chlorbufam; chlorfenac; chlorflurecol-methyl; chloridazon; chlorimuron ethyl; chlornitrofen; chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron; chlorthal-dimethyl; chlorthiamid; cinmethylin; cinosulfuron; clethodim; clodinafop and its ester derivatives (eg clodinafop-propargyl); clomazone; clomeprop; cloproxydim; clopyralid; cumyluron (JC 940); cyanazine; cycloate; Cyclosulfamuron (AC 104); cycloxydim; cycluron; cyhalofop and its ester derivatives (eg, butyl ester, DEH-112); cyperquat; cyprazine; cyprazole; daimuron; 2,4-DB; dalapon; desmedipham; Desmetryn; di-allate; dicamba; dichlobenil; dichloroprop; diclofop and its esters such as diclofop-methyl; diethatyl; difenoxuron; difenzoquat; diflufenican; dimefuron; dimethachlor; dimethametryn; dimethenamid (SAN-582H); dimethazone, clomazone; dimethipin; dimetrasulfuron, dinitramine; dinoseb; dinoterb; diphenamid; dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 77, ie 5-cyano-1- (1,1-dimethylethyl) -N-methyl-1H-pyrazole-4-carboxamide; endothal; EPTC; esprocarb; ethalfluralin; ethametsulfuron-methyl; Ethidimuron; ethiozin; ethofumesate; F5231, ie N- [2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -4,5-dihydro-5-oxo-1H-tetrazol-1-yl] -phenyl] -ethanesulfonamide; ethoxyfen and its esters (eg ethyl ester, HN-252); etobenzanide (HW 52); fenoprop; fenoxan, fenoxaprop and fenoxaprop-P and their esters, eg fenoxaprop-P-ethyl and fenoxaprop-ethyl; fenoxydim; fenuron; flamprop-methyl; flazasulfuron; fluazifop and fluazifop-P and their esters, eg fluazifop-butyl and fluazifop-P-butyl; fluchloralin; flumetsulam; flumeturon; flumiclorac and its esters (eg, pentyl ester, S-23031); flumioxazine (S-482); flumipropyn; flupoxam (KNW-739); fluorodifen; fluoroglycofen-ethyl; flupropacil (UBIC-4243); fluridone; flurochloridone; fluroxypyr; flurtamone; fomesafen; fosamine; furyloxyfen; glufosinate; glyphosate; halo safen; halosulfuron and its esters (eg, methyl ester, NC-319); haloxyfop and its esters; haloxyfop-P (= R-haloxyfop) and its esters; hexazinone; imazapyr; imazamethabenz-methyl; imazaquin and salts such as the ammonium salt; ioxynil; imazethamethapyr; imazethapyr; imazosulfuron; isocarbamid; isopropalin; isoproturon; isouron; isoxaben; isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MCPA; MCPB; mecoprop; mefenacet; mefluidide; metamitron; metazachlor; metham; methabenzthiazuron; methazole; methoxyphenone; methyldymron; metabenzuron, methobenzuron; metobromuron; metolachlor; metosulam (XRD 511); metoxuron; metribuzin; metsulfuron-methyl; MH; molinate; monalide; monolinuron; monuron; monocarbamide dihydrogen sulfates; MT 128, ie 6-chloro-N- (3-chloro-2-propenyl) -5-methyl-N-phenyl-3-pyridazineamine; MT 5950, ie N- [3-chloro-4- (1-methylethyl) phenyl] -2-methylpentanamide; naproanilide; napropamide; naptalam; NC 310, ie 4- (2,4-dichlorobenzoyl) -1-methyl-5-benzyloxypyrazole; neburon; nicosulfuron; nipyraclophen; nitralin; nitrofen; nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiargyl (RP-020630); oxadiazon; oxyfluorfen; paraquat; pebulate; pendimethalin; perfluidone; phenisopham; phenmedipham; picloram; pinoxaden; piperophos; piributicarb; pirifenop-butyl; pretilachlor; primisulfuron-methyl; procyazine; prodi amines; profluralin; proglinazine-ethyl; prometon; prometryne; propachlor; propanil; propaquizafop and its esters; propazine; propham; propisochlor; Propyzamide; prosulfalin; prosulfocarb; prosulfuron (CGA-152005); prynachlor; pyrazolinate; pyraclonil, pyrazon; pyrazosulfuron-ethyl; pyrazoxyfen; pyridate; pyrithiobac (KIH-2031); pyroxofop and its esters (eg propargyl esters); quinclorac; quinmerac; quinofop and its ester derivatives, quizalofop and quizalofop-P and their ester derivatives eg quizalofop-ethyl; quizalofop-P-tefuryl and -ethyl; renriduron; rimsulfuron (DPX-E 9636); S 275, ie 2- [4-chloro-2-fluoro-5- (2-propynyloxy) -phenyl] -4,5,6,7-tetrahydro-2H-indazole; secbumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, ie 2 - [[7- [2-chloro-4- (trifluoromethyl) phenoxy] -2-naphthalenyl] oxy] -propanoic acid and methyl ester; sulfentrazone (FMC-97285, F-6285); sulfazuron; sulfometuron-methyl; sulfosate (ICI-A0224); TCA; tebutam (GCP-5544); tebuthiuron; terbacil; terbucarb; terbuchlor; terbumeton; Terbuthylazine; terbutryn; TFH 450, ie, N, N-diethyl-3 - [(2-ethyl-6-methylphenyl) sulfonyl] -1H-1,2,4-triazole-1-carboxamide; thenylchlor (NSK-850); thiazafluron; thiazopyr (Mon-13200); thidiazimin (SN-24085); thiobencarb; thifensulfuron-methyl; tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triazofenamide; tribenuron-methyl; triclopyr; tridiphane; trietazine; trifluralin; triflusulfuron and esters (eg, methyl ester, DPX-66037); trimeturon; tsitodef; vernolate; WL 110547, ie 5-phenoxy-1- [3- (trifluoromethyl) -phenyl] -1H-tetrazole; UBH-509; D-489; LS 82-556; KPP-300; NC-324; NC-330; KH-218; DPX-N8189; SC-0774; Dowco-535; DK-8910; V-53482; PP-600; MBH-001; KIH-9201; ET-751; KIH-6127 and KIH-2023, KIH-485.

to Application are those in commercial Form present formulations optionally in the usual Diluted way e.g. for wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules by means of water. Dusty preparations, Soil or spreading granules and sprayable solutions are usually before use no longer diluted with other inert substances.

With the external conditions such as temperature, humidity, the type of herbicide used, et al varies the required application rate of the compounds of Formula (I). It can vary within wide limits, e.g. between 0.001 and 1.0 kg / ha or more of active substance, preferably However, they are between 0.005 and 750 g / ha.

The explain the following examples The invention.

A. Chemical examples

1. Preparation of 3-fluoro-5- (1-methyl-3-trifluoromethylpyrazol-5-yloxy) -nitrobenzene

30.00 g (189 mmol) of 3,5-difluoronitrobenzene were initially charged under nitrogen in 150 ml of N, N-dimethylformamide and at room temperature (RT) with 28.67 g (207 mmol) of K ₂ CO ₃ and 31.32 g (189 mmol) of 1-methyl -3- (trifluoromethyl) -pyrazol-5-one added. The mixture was heated at 85 ° C. for 33 h and at 100 ° C. for a further 3 h, cooled to RT and water was added to the reaction solution. It was extracted three times with ethyl acetate. The combined phases were washed with water and then dried over MgSO ₄ , filtered and concentrated. Column chromatography of the crude product gave 9.00 g of 3-fluoro-5- (1-methyl-3-trifluoromethylpyrazol-5-yloxy) -nitrobenzene as an orange-red oil.
¹ H-NMR: δ [CDCl ₃ ] 3.84 ppm (s, 3H), 6.07 (s, 1H), 7.20 (dt, 1H), 7.80 (m, 2H)

2. Preparation of 3- (1-methyl-5-trifluoromethylpyrazol-3-yloxy) -5- (3-trifluoromethylphenyloxy) -nitrobenzene

3.64 g (22.0 mmol) of 1-methyl-5- (trifluoromethyl) -pyrazol-3-one were initially charged under nitrogen in 100 ml of dimethylacetamide and treated at 0 ° C with 0.598 g (25.0 mmol) of NaH (80%). It was allowed to come to RT and 6.00 g (20.0 mmol) of 3-fluoro-5- (3-trifluoromethylphenyl) -nitrobenzene was added and heated for 2 h at 90 ° C and for a further 8 h at 130 ° C, cooled to RT and Water was added to the reaction solution and stirred for a few minutes. It was extracted twice with heptane / ethyl acetate (1: 1) and twice with ethyl acetate. The combined phases were washed with water and then dried over MgSO ₄ , filtered and concentrated. Column chromatography of the crude product gave 4.24 g of 3- (1-methyl-5-trifluoromethylpyrazol-3-yloxy) -5- (3-trifluoromethyl-phenyloxy) -nitrobenzene in the form of waxy crystals.
¹ H-NMR: δ [CDCl ₃ ] 3.92 ppm (s, 3H), 6.28 (s, 1H), 7.14 (t, 1H), 7.24 (dt, 1H), 7.34 (s, 1H), 7.45-7.60 ( m, 2H), 7.75 (t, 1H).

3. Preparation of 3- (1-methyl-5-trifluoromethylpyrazol-3-yloxy) -5- (3-trifluoromethylphenyloxy) -aniline

4.00 g (9.0 mmol) of 3- (1-methyl-5-trifluoromethylpyrazol-3-yloxy) -5- (3-trifluoromethylphenyloxy) -nitrobenzene, 5.00 g (45.0 mmol) of ammonium formate and 0.50 g (4.0 mmol) of Pd (OH) ₂ on carbon (20%) were placed under nitrogen atmosphere in 100 ml of methanol and erwämt for 90 min at 70 ° C. It was cooled to rt, the reaction solution was filtered, concentrated and 3.75 g of 3- (1-methyl-5-trifluoromethylpyrazol-3-yloxy) -5- (3-trifluoromethylphenyloxy) -aniline as a yellow oil.
¹ H-NMR: δ [CDCl ₃ ] 3.88 ppm (s, 3H), 6.08 (t, 1H), 6.15 (t, 1H), 6.17 (s, 1H), 6.23, (t, 1H), 7.20 (i.e. , 1H), 7.26 (s, 1H), 7.34 (d, 1H), 7.43 (t, 1H).

4. Preparation of 1- (1-methyl-5-trifluoromethylpyrazol-3-yloxy) -3- (3-trifluoromethylphenyloxy) benzene

0.215 g of 3- (1-methyl-5-trifluoromethylpyrazol-3-yloxy) -5- (3-trifluoromethylphenyloxy) -aniline and 0.159 g (2.0 mmol) of n-butylnitrite were placed under nitrogen in 5 ml of THF and dried for 3-4 h to 40 ° C. It was cooled to RT, water was added to the reaction solution and stirred for a few minutes and extracted twice with ethyl acetate. The combined phases were washed with water and then dried over MgSO ₄ , filtered and concentrated. Column chromatography of the crude product gave 60 mg of 1- (1-methyl-5-trifluoromethylpyrazol-3-yloxy) -3- (3-trifluoromethylphenyloxy) benzene as a yellow oil.
¹ H-NMR: δ [CDCl ₃ ] 3.85 ppm (s, 3H), 6.08 (s, 1H), 6.77 (dt, 1H), 6.80 (t, 1H), 6.90, (dt, 1H), 7.20 (dt , 1H), 7.28-7.38 (m, 3H), 7.43 (t, 1H).

5. Preparation of 3- (1-methyl-5-trifluoromethylpyrazol-3-yloxy) -5- (3-trifluoromethyl-phenyloxy) -fluorobenzene

0.185 g (2.0 mmol) of nitrosyltetrafluoroborate were added to 0.220 g of 3- (1-methyl-5-trifluoromethylpyrazol-3-yloxy) -5- (3-trifluoromethylphenyloxy) -aniline dissolved in 5 ml of chlorobenzene under protective gas at 0.degree Stirred at RT for 30 min and heated to 90 ° C for 3 h. It was cooled to RT, added water, stirred for a few minutes and extracted twice with ethyl acetate. The combined phases were washed with water and then dried over MgSO ₄ , filtered and concentrated. Column chromatography of the crude product gave 40 mg of 3- (1-methyl-5-trifluoromethylpyrazol-3-yloxy) -5- (3-trifluoromethyl-phenyloxy) -fluorobenzene as a yellow oil.
¹ H-NMR: δ [CDCl ₃ ] 3.85 ppm (s, 3H), 6.21 (s, 1H), 6.43 (dt, 1H), 6.58 (s, 1H), 6.63, (dt, 1H), 7.22 (dt , 1H), .7.30 (s, 1H), 7.38-7.50 (bm, 2H).

6. Preparation of 3- (1-methyl-5-trifluoromethylpyrazol-3-yloxy) -5- (1-methyl-3-trifluoromethylpyrazol-5-yloxy) -fluorobenzene

126 mg of 1-methyl-5- (trifluoromethyl) -pyrazol-3-one were initially introduced under protective gas in 5 ml of dimethylacetamide and treated at 0 ° C with 27 mg NaH (80%). It was allowed to come to RT and 200 mg of 5- (1-methyl-3-trifluoromethylpyrazol-5-yloxy) -1,3-difluorobenzene and catalytic amounts of copper iodide were added and the mixture was heated at 150 ° C. for 6 h, cooled to RT, added water and stirred for a few minutes. It was extracted three times with ethyl acetate. The combined phases were washed with water, dried over MgSO ₄ , filtered and concentrated. Column chromatography of the crude product gave 200 mg of 3- (1-methyl-5-trifluoromethylpyrazol-3-yloxy) -5- (1-methyl-3-trifluoromethylpyrazol-5-yloxy) -fluorobenzene as a yellow oil.
¹ H-NMR: δ [CDCl ₃ ] 3.78 ppm (s, 3H), 3.91 (s, 3H), 6.01 (s, 1H), 6.24 (s, 1H), 6.58 (dt, 1H), 6.70 (m, 2H).

7. Preparation of 3- (1-methyl-5-trifluoromethylpyrazol-3-yloxy) -5- (3-trifluoromethylphenyloxy) -chlorobenzene

0.400 g of 3- (1-methyl-5-trifluoromethylpyrazol-3-yloxy) -5- (3-trifluoromethylphenyloxy) -aniline were dissolved in 5 ml of methylene chloride and treated at 0-5 ° C with 0.569 g (6.0 mmol) of copper (I. ) and then treated with 0.593 g (6.0 mmol) of n-butyl nitrite and stirred for 2-3 h at 0-5 ° C. The mixture was allowed to come to RT overnight, water was added to the reaction solution and stirred for a few minutes and extracted twice with methylene chloride. The combined phases were washed with water and then dried over MgSO ₄ , filtered and concentrated. Column chromatography of the crude product gave 60 mg of 1- (1-methyl-5-trifluoromethylpyrazol-3-yloxy) -3- (3-trifluoromethyl-phenyloxy) -chlorobenzene as an orange oil.
¹ H-NMR: δ [CDCl ₃ ] 3.84 ppm (s, 3H), 6.18 (s, 1H), 6.80 (m, 2H), 6.91 (dt, 1H), 7.18 (dt, 1H), 7.28-7.50 ( m, 3H).

The listed in the following tables Examples were prepared analogously to the above methods or are available analogously to the above methods.

Tabelle B: Erfindungsgemäße Verbindungen der allgemeinen Formel (I), worin die Substituenten und Symbole folgende Bedeutungen haben:

Tabelle C: Erfindungsgemäße Verbindungen der allgemeinen Formel (I), worin die Substituenten und Symbole folgende Bedeutungen haben:

Tabelle D: Erfindungsgemäße Verbindungen der allgemeinen Formel (I), worin die Substituenten und Symbole folgende Bedeutungen haben:

The abbreviations used mean
Et = ethyl
Me = Methyl Table A: Compounds of the general formula (I) according to the invention, in which the substituents and symbols have the following meanings:

Table B: Compounds of the general formula (I) according to the invention, in which the substituents and symbols have the following meanings:

Table C: Compounds of the general formula (I) according to the invention, in which the substituents and symbols have the following meanings:

Table D: Compounds of the general formula (I) according to the invention, in which the substituents and symbols have the following meanings:

B. Formulation Examples

1. Dusts

One dusts is obtained by adding 10 parts by weight of a compound of the general Formula (I) and 90 parts by weight of talc mixed as inert and in a hammer mill crushed.

2. Dispersible powder

One water-dispersible, wettable powder is obtained by 25 parts by weight of a compound of the general formula (I), 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight lignosulfonic acid potassium and 1 part by weight of oleoylmethyltaurine acid Mix sodium as wetting and dispersing agent and grind in a pin mill.

3. Dispersion concentrate

An easily water-dispersible dispersion concentrate is obtained by mixing 20 parts by weight of a compound of general formula (I), 6 parts by weight of alkylphenol polyglycol ether (Triton ^® X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight Parts of paraffinic mineral oil (boiling range, for example, about 255 to about 277 ° C) mixed and ground in a ball mill to a fineness of less than 5 microns.

4. Emulsifiable concentrate

One emulsifiable concentrate is obtained from 15 parts by weight of a Compound of general formula (I), 75 parts by weight of cyclohexanone as a solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier.

5. Water dispersible granules

A water-dispersible granule is obtained by
75 parts by weight of a compound of general formula (I),
10 parts by weight of a lignosulfonic acid calcium,
5 parts by weight of a sodium lauryl sulfate,
3 parts by weight of a polyvinyl alcohol and
7 parts by weight of a kaolin
milled, ground on a pin mill and granulated the powder in a fluidized bed by spraying water as Granulierflüssigkeit.

A water-dispersible granule is also obtained by
25 parts by weight of a compound of general formula (I),
5 parts by weight of sodium 2,2'-dinaphthylmethane-6,6'-disulfonate,
2 parts by weight of an oleoylmethyltaurine acid,
1 part by weight of a polyvinyl alcohol,
17 parts by weight of a calcium carbonate and
50 parts by weight of a water
Homogenized on a colloid mill and pre-crushed, then ground on a bead mill and the suspension thus obtained in a spray tower by means of a Einstoffdüse atomized and dried.

C. Biological examples

1. Herbicidal action against Weeds in pre-emergence

seed of monocotyledonous and dicotyledonous weed plants are found in cardboard pots in sandy loam soil covered and covered with soil. The in shape of wettable powders or emulsion concentrates Compounds are then treated as an aqueous suspension or emulsion with a water application amount of 600 to 800 l / ha in a dosage of 1,000 g per hectare the surface the cover soil applied. After treatment, the pots are in the greenhouse placed and kept under good growth conditions for the weeds. The optical assessment of the plant or run-in damage takes place after emergence of the test plants after a trial period from 3 to 4 weeks compared to untreated controls. To 3 to 4 weeks life of the test plants in the greenhouse Under optimal growth conditions, the effect of the compounds compared to compounds disclosed in the prior art are, rated. As the results of comparison table 1 show, show the selected ones Compounds of the invention thereby a better herbicidal activity against a broad spectrum economically important mono- and dicotyledonous harmful plants than those disclosed in the prior art.

2. Herbicidal action against Harmful plants in postemergence

seed of monocotyledonous and dicotyledonous weeds are found in cardboard pots in sandy clay soil, covered with soil and in the greenhouse attracted under good growing conditions. Two to three weeks after sowing, the test plants are in trefoil studies treated. Formulated as wettable powders or as emulsion concentrates Compounds of the invention are converted with a water application amount of 600 to 800 l / ha in a dosage of the equivalent of 1000g per hectare on the surface the green Sprayed plant parts. After 3 to 4 weeks life of the test plants in the greenhouse Under optimal growth conditions, the effect of the compounds compared to compounds disclosed in the prior art are, rated. As the results of comparison charts 2 to 4 show the selected ones Compounds of the invention thereby a better herbicidal activity against a broad spectrum economically important monocotyledonous and dicotyledonous harmful plants those disclosed in the prior art.

3. crop compatibility

Aus dem Stand der Technik (WO 2003/051846) bekannte Verbindungen:

In further greenhouse experiments, seeds of barley and monocotyledonous and dicotyledonous weeds are placed in sandy loam soil, covered with soil and placed in the greenhouse until the plants have developed two to three true leaves. The treatment with the compounds of the formula (I) according to the invention and in comparison with those disclosed in the prior art then takes place as described above under point 1. Four to five weeks after the application and service life in the greenhouse it is determined by means of optical Bonitur that compounds of the invention, unlike the compounds disclosed in the prior art leaves the crop undamaged even at higher drug doses. Compounds of the invention

From the prior art (WO 2003/051846) known compounds:

AMARE

Amaranthus retroflexus

AVESA

Avena fatua

LOLMU

Lolium multiflorum

SETVI

Setaria viridis

SINAL

Sinapis arvensis

STEME

Stellaria media

The abbreviations used in the following comparison tables mean:

AMARE

Amaranthus retroflexus

AVESA

Avena fatua

LOLMU

Lolium multiflorum

SETVI

Setaria viridis

SINAL

Sinapis arvensis

STEMS

Stellaria media

Comparison Chart 1, pre-emergence

Comparison Chart 2, postemergence

Comparison Chart 3, postemergence

Comparison Chart 4, postemergence

Claims (13)

Pyrazolyloxyphenylderivate of formula (I) and their salts

wherein the substituents and indices have the following meanings: R ¹ is hydrogen, bromine, chlorine, fluorine, iodine or methylthio; R ² is trifluoromethyl, difluoromethyl or chlorodifluoromethyl R ³ is methyl or ethyl; A is a radical from the group comprising the radicals A1 to A4

R ⁴ is fluoromethyl, difluoromethyl, trifluoromethyl, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chloro or cyano; R ⁵ is hydrogen, (C ₁ -C ₈ ) -alkyl, bromine, chlorine, fluorine, iodine or cyano, and R ⁶ is (C ₁ -C ₈ ) -alkyl. Pyrazolyloxyphenyl derivatives according to claim 1, wherein R ^{1 represents} hydrogen, bromine, chlorine, fluorine, iodine or methylthio; R ² is trifluoromethyl or difluoromethyl; R ³ is methyl or ethyl; A is a radical from the group comprising the radicals A1 to A4; R ⁴ is difluoromethyl trifluoromethyl, difluoromethoxy, trifluoromethoxy, chloro or cyano; R ⁵ is hydrogen, fluorine or chlorine R ⁶ is methyl or ethyl. Pyrazolyloxyphenyl derivatives according to claim 1 or 2, wherein R ^{1 represents} hydrogen, bromine, chlorine, fluorine or iodine; R ² is trifluoromethyl or difluoromethyl; R ³ is methyl or ethyl; A is a radical from the group comprising the radicals A1 to A4; R ⁴ is difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, chloro or cyano; R ⁵ is hydrogen or fluorine; R ⁶ is methyl. Pyrazolyloxyphenyl derivatives according to any one of claims 1 to 3, wherein R ^{1 represents} hydrogen, bromine, chlorine, fluorine or iodine; R ² is trifluoromethyl or difluoromethyl; R ³ is methyl or ethyl; A is the radical A1; R ⁴ is difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, chloro or cyano; R ⁵ is hydrogen or fluorine. Pyrazolyloxyphenyl derivatives according to any one of claims 1 to 3, wherein R ^{1 represents} hydrogen, bromine, chlorine, fluorine or iodine; R ² is trifluoromethyl or difluoromethyl; R ³ is methyl or ethyl; A is the radical A2; R ⁴ is difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, chloro or cyano. Pyrazolyloxyphenyl derivatives according to any one of claims 1 to 3, wherein R ^{1 represents} hydrogen, bromine, chlorine, fluorine or iodine; R ² is trifluoromethyl or difluoromethyl; R ³ is methyl or ethyl; A is the radical A3; R ⁴ is difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, chloro or cyano. Pyrazolyloxyphenyl derivatives according to any one of claims 1 to 3, wherein R ^{1 represents} hydrogen, bromine, chlorine, fluorine or iodine; R ² is trifluoromethyl or difluoromethyl; R ³ is methyl or ethyl; A means the remainder A4; R ⁴ is difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, chloro or cyano; R ⁶ is methyl. Herbicidal agent, characterized by a herbicide effective content of at least one compound of the general Formula (I) according to a the claims 1 to 7. A herbicidal composition according to claim 8 in admixture with Formulation auxiliaries. Method of combating unwanted Plant, characterized in that an effective amount of at least a compound of general formula (I) according to any one of claims 1 to 7 or a herbicidal composition according to claim 8 or 9 on the plants or on the place of the unwanted Plant growth applied. Use of compounds of the general formula (I) according to any one of claims 1 to 7 or herbicidal compositions according to claim 8 or 9 for controlling unwanted Plants. Use according to claim 11, characterized that the Compounds of general formula (I) for controlling unwanted Plants are used in crops of crops. Use according to claim 12, characterized that the Crop plants are transgenic crops.